JPH11263835A - Fuel composition containing polyamine of poly(oxyalkylene)aromatic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fuel composition which suppresses the buildup of deposits in an engine by incorporating a polyamine-containing poly(oxyalkylene)aromatic ester and its soluble salt in a hydrocarbon fuel. SOLUTION: There is provided a polyamine-containing poly(oxyalkylene) aromatic ester having a molecular weight of 600-10,000 and represented by formula I and is used in an amount of 50-2,500 ppm based on the weight of a hydrocarbon fuel. It is also used in the form of a concentrate having a concentration of 10-70 wt.% and prepared by using an inert oleophilic organic solvent having a boiling point of 60-205 deg.C. The aromatic ester is produced by esterifying an aromatic carboxylic acid represented by formula II with a poly(oxy)alkylene alcohol at 70-160 deg.C in the presence of an acidic catalyst and is converted into a soluble salt by protonating its amine moiety with an organic acid. In the formulae, R1 is a 2-40C polyamine moiety having 2-12 aminic nitrogen atoms; R2 and R3 are each H or a 1-6C lower alkyl; R4 and R7 are each H, a 1-100C alkyl, phenyl, or the like; y is 5-100; and W is a halogen or nitro.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamine of a poly (oxyalkylene) aromatic ester and to a fuel composition containing the polyamine of a poly (oxyalkylene) aromatic ester. In particular, the present invention relates to a poly (oxyalkylene) aromatic ester having a polyamine moiety connected to an aromatic ring, and use of the ester in a fuel composition for preventing or suppressing accumulation of deposits inside an engine. .

[0002]

2. Description of the Related Art In an automobile engine, it is known that hydrocarbon fuel oxidized or polymerized deposits easily adhere to surfaces of engine parts such as a carburetor port, a throttle section, a fuel injection section, an intake port, and an intake valve. Have been. These deposits, even in relatively small quantities, often cause significant operating performance problems such as engine shutdown and reduced acceleration. In addition, engine deposits degrade vehicle fuel economy and increase pollutants in exhaust gas. Therefore, the development of deposition control additives to prevent or control such buildup of deposits, as well as effective fuel detergents, is extremely important and many substances are already known. .

[0003] For example, aminophenols are known to function as detergents, dispersants, antioxidants and corrosion inhibitors when used in fuel compositions. For example, 19
US Patent No. 432002, issued March 16, 1982
No. 1 (RM Lang) discloses aminophenols having a substituent of at least 30 carbon atoms based on at least one substantially saturated hydrocarbon. This patent specification states that the aminophenol described above can provide effective and favorable characteristics when used in a lubricant containing lubricating oil as a main component or a usual liquid fuel. In addition, a similar aminophenol was prepared in 1982.
Related U.S. Pat. No. 4,432,023, issued Mar. 16, 2002
No. 0 (RM Lang).

Similarly, US Pat. No. 3,149,933 (K. Rei et al.), Issued Sep. 22, 1964, describes the use of hydrocarbon-substituted aminophenols as stabilizers in liquid fuels. ing.

[0005] US Patent No. 4,386,939 (R. M. Lang) issued June 7, 1983 describes a compound in which the heteroatom is a single oxygen, sulfur or nitrogen, such as ethylene oxide. Disclosed are nitrogen-containing compositions obtained by reacting at least one membered or four-membered heterocycle with an aminophenol. The patent describes that the nitrogen-containing composition is useful as a lubricant or fuel additive.

Furthermore, it has recently been shown that the use of certain poly (oxyalkylene) esters in fuel compositions can reduce engine internal deposits. For example, US Pat. No. 52, issued May 18, 1993
No. 11721 (RL Sang et al.) Disclose RCO
A fat-soluble polyether additive comprising a reaction product of an acid represented by OH (R is a hydrocarbon group having 6 to 27 carbon atoms) and a polyether polyol is disclosed. It is described in the above specification that the poly (oxyalkylene) ester is effective in suppressing the formation of carbonaceous deposits and the scattering of fuel when used as an automotive fuel composition.

[0007] Poly (oxyalkylene) esters of aminobenzoic acid and nitrobenzoic acid are already known.
For example, U.S. Patent No. 2 issued August 2, 1955
714607 (M. Matter) discloses polyethoxy esters of aminobenzoic acid, nitrobenzoic acid and other homocyclic acids. It is described in the above specification that this polyethoxy ester has excellent drug efficacy and can be used as an anesthetic, an antispasmodic, a central nervous system stimulant or a bacteriostat. Further, similar polyethoxy esters are disclosed in U.S. Pat. Nos. 2,714,608 and 2,714,609, both of which are M. Matter.

Also, US Pat. No. 5,090,914 issued on Feb. 25, 1992 (DT Riadan et al.)
The specification describes poly () having an amino or hydrazinocarbonyl substituent on the aromatic ring and further linking the aromatic ring and the poly (oxyalkylene) moiety with an ester, amide, carbamate, urea or ether. Oxyalkylene) aromatic compounds are disclosed. This compound
It is described in the above specification that it is effective for modifying macromolecular species such as proteins and enzymes. Nos. 5,081,295, 5,103,039 and 51.
No. 57099 (DT Riadan et al.) Discloses a similar poly (oxyalkylene) aromatic compound.

US Pat. No. 4,328,322 (RC Baron), issued Sep. 22, 1980, includes:
Amino and nitrobenzoate esters of multimeric polyols such as poly (ethylene) glycol are disclosed. This compound is used to make a synthetic polymer by reaction with a polyisocyanate. Similar compounds are described in US Pat. No. 451, issued May 7, 1985.
No. 5981 (K. Otani) and US Pat.
Nos. 39775 and 5086153 (both are Y. Oyaz).

[0010] US Patent No. 5,407,452 (RE Chapec), issued April 18, 1995, describes a nitro, amino, N-alkylamino or N, N-dialkylamino moiety on an aromatic ring. A poly (oxyalkylene) aromatic ester having the formula: This compound is described in the above patent as being effective as a fuel additive to prevent or control engine deposits.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a substance which is effective in preventing or suppressing accumulation of deposits in an engine.

[0012]

Means for Solving the Problems The present inventors have found that a poly (oxyalkylene) aromatic ester having a polyamine moiety on an aromatic ring is added to a fuel composition as a fuel additive.
It has been found to be extremely effective in reducing engine deposits, especially deposits in the intake valve section.

That is, the present invention resides in a novel compound represented by the following formula (I) and a fuel-soluble salt thereof.

[0014]

Embedded image

(R ₁ has 2 to 12 amine nitrogen atoms;
Represents a polyamine moiety having 2 to 40 carbon atoms, the polyamine moiety being connected to the aromatic ring via one of the amine nitrogen atoms; R ₂ and R ₃ are each —O—CHR ₂ — C
Independently for each HR ₃ -unit, and each independently of one another, represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms; R ₄ represents a hydrogen atom, an alkyl group having 1 to 100 carbon atoms, a phenyl group, Represents an aralkyl group having 7 to 100 carbon atoms, an alkaryl group having 7 to 100 carbon atoms, or an acyl group having the following formula; y represents an integer of 5 to 100)

[0016]

Embedded image

(R ₅ is an alkyl group having 1 to 30 carbon atoms, a phenyl group, an aralkyl group having 7 to 36 carbon atoms,
Or an alkaryl group having 7 to 36 carbon atoms).

The present invention also relates to a polyamine-containing polyamine represented by the above formula, which contains a hydrocarbon having a boiling point in the range of gasoline or diesel oil as a main component and is effective in suppressing the formation of engine deposits. There are also fuel compositions containing (oxyalkylene) aromatic esters. In addition, the present invention provides a boiling point of 65 ° C (150 ° F) to 205 ° C.
(400 ° F.) in a fuel concentrate comprising an inert and stable lipophilic organic solvent and 10-70% by weight of a polyamine-containing poly (oxyalkylene) aromatic ester of the above formula. There is also.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The compound provided by the present invention is a polyamine-containing poly (oxyalkylene) aromatic ester represented by the following general formula (I).

[0020]

Embedded image

(R ₁ , R ₂ , R ₃ , R ₄ and y have the meaning described above)

In the above formula (I), R ₁ represents a polyamine moiety having about 2 to 12 amine nitrogen atoms and about 2 to 40 carbon atoms, wherein the polyamine moiety is one of the amine nitrogen atoms. Is connected to the aromatic ring. Preferably, R ₁ represents a polyamine moiety derived from a polyalkylene polyamine having about 2 to 12 nitrogen atoms and about 2 to 24 carbon atoms, and more preferably the following (II)
It represents a polyamine moiety derived from the polyalkylene polyamine represented by the formula.

[0023]

Embedded image H ₂ N— (R ₆ NH) _z —H (II)

Here, R ₆ represents an alkylene group having about 2 to 6 carbon atoms, and z represents an integer of 1 to about 4. R
Most preferably, ₁ is a polyamine moiety derived from ethylenediamine or diethylenetriamine.

It is preferred that one of R ₂ and R ₃ is a lower alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom. More preferably, one of R ₂ and R ₃ is a methyl group or an ethyl group, and the other is a hydrogen atom. Most preferably, one of R ₂ and R ₃ is an ethyl group and the other is a hydrogen atom.

R ₄ is preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, or an alkylphenyl group having an alkyl group having 2 to 24 carbon atoms, and particularly preferably, a hydrogen atom or an alkyl group having 4 to 12 carbon atoms. Or an alkylphenyl group having an alkyl group having 4 to 12 carbon atoms. Among them, R ₄ is most preferably an alkylphenyl group having an alkyl group having 4 to 12 carbon atoms.

R ₅ preferably represents an alkyl group having 4 to 12 carbon atoms. y is preferably an integer of 8 to 50, and more preferably an integer of 10 to 30.

In a preferred embodiment of the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention, R ₁ is a polyamine moiety derived from ethylenediamine or diethylenetriamine; one of R ₂ and R ₃ is a methyl group or an ethyl group. R ₄ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms; and y is an integer of 8 to 50. Is an ester.

[0029] A further preferred embodiment, a polyamine unit R ₁ is derived from ethylenediamine or diethylenetriamine; one of R ₂ and R ₃ is a methyl group or an ethyl group and the other is hydrogen atom; R ₄ is a hydrogen atom An alkyl group having 2 to 24 carbon atoms or an alkylphenyl group having an alkyl group having 2 to 24 carbon atoms; and an ester wherein y is an integer of 8 to 50.

[0030] Especially preferred embodiments, a polyamine unit R ₁ is derived from ethylenediamine; whereas a methyl group or an ethyl group R ₂ and R _3, the other is a hydrogen atom; R ₄ is a hydrogen atom, An alkyl group having 2 to 24 carbon atoms or an alkylphenyl group having an alkyl group having 2 to 24 carbon atoms; and an ester wherein y is an integer of 10 to 30.

The polyamine group linked to the aromatic ring of the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention is particularly preferably located para to the poly (oxyalkylene) moiety.

The polyamine-containing poly (oxyalkylene) aromatic ester of the present invention is usually used at a temperature (about 200 ° C.) at which an intake valve (intake valve) of an engine operates.
It has a molecular weight sufficient to become non-volatile at about 250 ° C.). Typical molecular weights are between about 600 and 10,000, preferably between about 1000 and 3000.

Generally, the polyamine-containing poly (oxyalkylene) aromatic esters of the present invention have an average of about 5
It has from about 100 to about 100, preferably about 8 to 50, more preferably about 10 to 30 oxyalkylene units.

The fuel-soluble salt of the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention can be easily synthesized, and is effective in preventing and suppressing accumulation of deposits in an engine. Preferred salts can be obtained, for example, by protonating the amino moiety with a strong organic acid such as an alkyl or aryl sulfonic acid. Particularly, salts derived from toluenesulfonic acid and methanesulfonic acid are preferred.

[Meaning of Terms] The terms used herein have the following meanings unless otherwise specified. "amino"
Means -NH ₂ group, "alkyl" refers to alkyl groups straight or branched chain. "Lower alkyl" means primary, secondary and tertiary alkyl groups having 1 to 6 carbon atoms. Typical lower alkyls include, for example, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl and the like. "Lower alkoxy" means a group -OR _a (where R _a is a lower alkyl group). Typical lower alkoxy groups include, for example, methoxy, ethoxy, and the like. Further, the “oxyalkylene unit” is an ether moiety represented by the following general formula.

[0036]

Embedded image

(R _b and R _c each independently represent a hydrogen atom or a lower alkyl group)

"Poly (oxyalkylene)" is a polymer or oligomer represented by the following general formula.

[0039]

Embedded image

(R _b and R _c have the same meaning as described above;
x is an integer greater than 1)

When the number of poly (oxyalkylene) units in a particular poly (oxyalkylene) compound is described, it means the average number of poly (oxyalkylene) units in the compound, unless otherwise specified. By "fuel" or "hydrocarbon fuel" is meant a normal liquid hydrocarbon having a boiling point in the same range as gasoline and diesel oil.

[General Synthesis Method] The polyamine-containing poly (oxyalkylene) aromatic ester of the present invention can be obtained by the following method. Those skilled in the art will appreciate that given the typical and preferred conditions described below (eg, reaction temperature, time, mole ratios of reactants, solvents, pressures, etc.), other conditions may be used unless otherwise stated. can do. The optimum reaction conditions vary depending on the reactants, the solvent and the like, but those skilled in the art can determine the conditions by a known method.

In performing the following synthesis reaction, it may be necessary to protect a specific functional group. In this case, the protecting group protects the functional group from undesired reactions so that the desired chemical change occurs, or prevents the undesired chemical change of a specific functional group by other functional groups or reagents. The choice of protecting groups to be used to protect a particular functional group is straightforward for a person skilled in the art. In the synthesis reactions described below, it is preferable to protect the hydroxyl group with benzyl or t-butyldimethylsilyl ether, if necessary. Methods for introducing and removing various protecting groups are described, for example, in T.W. W. Green and P.I. G. FIG. M. Protective Group by Utz
s in Organic Synthesis ”(2nd edition, Wiley, New York,
1991).

The synthesis of the poly (oxyalkylene) aromatic ester of the present invention represented by the following formula (III) will be described below.

[0045]

Embedded image

(R ₁ , R ₂ , R ₃ and y have the same meaning as described above, and R ₇ is alkyl, phenyl, aralkyl or alkaryl)

The above compound is firstly represented by the following formula (IV)
Aromatic carboxylic acid represented by:

[0048]

Embedded image

(W is a halogen atom, preferably a fluorine atom or a nitro group), and is converted to a poly (oxyalkylene) alcohol represented by the following formula (V):

[0050]

Embedded image

(R ₂ , R ₃ , R ₇ and y have the same meanings as described above) by esterification under ordinary conditions.

The obtained compound is represented by the following formula (VI).

[0053]

Embedded image

(W, R ₂ , R ₃ , R ₇ and y have the same meaning as described above).

The above reaction can be carried out, for example, by reacting a poly (oxyalkylene) alcohol of the formula (V) with 0.9 to 1.5 molar equivalents of an aromatic carboxylic acid (IV) in the presence of an acidic catalyst. The reaction can be carried out at 70 ° C. to about 160 ° C. for about 0.5 to 48 hours. Suitable acidic catalysts include, for example, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid and the like. This reaction can be performed in the presence or absence of an inert solvent such as toluene and xylene. The water produced by the reaction
It can be removed continuously by known methods, for example, azeotropic distillation with an inert solvent such as xylene.

Alternatively, the poly (oxyalkylene) aromatic ester of formula (VI) is a poly (oxyalkylene)
The alcohol (V) may be synthesized by reacting with a halide of the aromatic carboxylic acid (IV), for example, chloride, bromide or the like.

In general, the carboxylic acid moiety of formula (IV)
By reacting (IV) with a halide of an inorganic acid such as thionyl chloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, or oxalyl chloride, it is converted to an acyl halide. This can be accomplished, for example, using 1 to about 5 molar equivalents of an inorganic acid halide, (IV) alone or in an inert solvent such as diethyl ether at a temperature ranging from about 20 ° C to 80 ° C for 1 hour to 1 hour. The reaction can be performed for about 48 hours. In this reaction, a catalyst such as N, N-dimethylformamide may be used.

The poly (oxyalkylene) aromatic ester of the formula (VI) can be obtained by the reaction of a halide derived from (IV) with a poly (oxyalkylene) alcohol (V). This can be accomplished, for example, by treating (V) with about 0.9 to 1.5 molar equivalents of the halide in an inert solvent such as toluene, dichloromethane, diethyl ether, at a temperature in the range of about 25 ° C to about 150 ° C. And the reaction can be carried out. The reaction time is generally about 0.5-4.
8 hours. In order to neutralize the acid generated during the reaction, it is preferable to carry out the reaction in the presence of a sufficient amount of an amine such as triethylamine, di (isopropyl) ethylamine, pyridine, or 4-dimethylaminopyridine.

The aromatic carboxylic acid of the formula (IV) used in the above reaction may be a known compound or may be synthesized from a known compound by a conventional method. Examples of suitably used aromatic carboxylic acids are as follows, but the present invention is not limited thereto. That is, 2-bromo-, 2-chloro-, 2-iodo-, 2-
Fluoro- or 2-nitrobenzoic acid; 4-bromo-, 4-chloro-, 4-iodo-, 4-fluoro- or 4-nitrobenzoic acid. A preferred aromatic carboxylic acid is 4-fluorobenzoic acid.

The poly (oxyalkylene) alcohol of formula (V) is also a known compound that can be synthesized by a conventional method. Suitable methods for synthesizing such compounds are described, for example, in US Pat. Nos. 2,782,240 and 2,841,479.

The poly (oxyalkylene) alcohol of the formula (V) is obtained by converting the alkoxide or phenoxide represented by the following formula (VII) to the formula (VIII) represented by the following formula (VIII) in an amount of about 5 to about 100 molar equivalents. It is preferable to synthesize by reacting with an alkylene oxide (epoxide).

[0062]

Embedded image R ₇ OM (VII)

(R ₇ has the same meaning as described above, and M represents a metal cation such as lithium, sodium, potassium, etc.)

[0064]

Embedded image

(R ₂ , R ₃ and y have the same meaning as described above)

The metal salt (VII) can be prepared, for example, by converting the corresponding hydroxide (R ₇ OH) into a strong base such as sodium hydroxide, potassium hydroxide or sodium amide in an inert solvent such as toluene or xylene. And in a state substantially free of moisture at a temperature of about -10 ° C to about 120 ° C for about 0.25 to 3 hours.

The metal salt (VII) is generally not isolated
The poly (oxyalkylene) alcohol (V) is obtained through neutralization by directly reacting with the alkylene oxide of (VIII). This polymerization reaction is carried out, for example, in an inert solvent substantially free of moisture at a temperature of about 30 ° C. to about 150 ° C. for about 2 to 120 hours. Preferred solvents are toluene, xylene and the like. The reaction is carried out at a pressure sufficient to maintain the reaction raw materials and the solvent, but is preferably carried out at normal pressure or atmospheric pressure.

The amount of alkylene oxide used in the above reaction generally depends on the number of oxyalkylene units in the desired product. Alkylene oxide (VIII)
A typical molar ratio of the to the metal salt (VII) is about 5: 1 to 1
It ranges from 100: 1, preferably from about 8: 1 to 50: 1, more preferably from about 10: 1 to 30: 1.

Examples of the alkylene oxide include butylene oxide such as ethylene oxide, propylene oxide, 1,2-butylene oxide (1,2-epoxybutane) and 2,3-butylene oxide (2,3-epoxybutane), and pentylene oxide. Lenoxide, hexylene oxide, octylene oxide and the like can be mentioned. Preferred alkylene oxides are propylene oxide and 1,2-butylene oxide.

In the above polymerization reaction, a single alkylene oxide such as propylene oxide can be used, and in such a case, the obtained product is a homopolymer such as a poly (oxypropylene) polymer. The product may be a copolymer. For example, a random copolymer is synthesized by reacting a mixture of an alkylene oxide such as a mixture of propylene oxide and 1,2-butylene oxide with a metal salt (VII). Is also good. Copolymers having blocks of oxyalkylene units are also suitable for the present invention. The block copolymer can be obtained by first reacting the metal salt (VII) with the first alkylene oxide and then reacting it with another alkylene oxide in any order or repeatedly.

Particularly preferred copolymers usable in the present invention are poly (oxyalkylene) copolymers having 1 to about 10, preferably about 2 to 5 oxyethylene unit-terminated poly (oxyalkylene) moieties. It is. This copolymer can be esterified more easily than one having an alkyl branch at the terminal oxyalkylene unit. The above-mentioned copolymer is obtained, for example, by reacting a metal salt (VII) with an alkylene oxide of the formula (VIII) such as propylene oxide or 1,2-butylene oxide, and at the terminal of a block of the obtained oxyalkylene unit, It can be obtained by connecting oxyethylene units by adding ethylene oxide.

The poly (oxyalkylene) alcohol (V) can be obtained from S.I. Inoue, T.W. Goda et al.'S Encyclopedia of
Polymer Science and Engineering, 2nd edition, 412-
As described on page 420 (J. Wiley and Sons, New York), it may be synthesized by living polymerization or the like. This method is suitable for synthesizing a poly (oxyalkylene) alcohol in which R ₂ and R ₃ in the formula (V) are both alkyl groups.

The alkoxide or phenoxide metal salt (VII) used in the above reaction is generally derived from the corresponding hydroxide R ₇ OH, as described above. Preferred hydroxides are linear or branched aliphatic alcohols having 1 to about 100 carbon atoms, or phenolic compounds of formula (IX).

[0074]

Embedded image

(R ₈ represents an alkyl group having 1 to about 100 carbon atoms, and R ₉ represents a hydrogen atom.
R ₈ and R ₉ each independently represent an alkyl group having 1 to about 50 carbon atoms)

The linear or branched aliphatic alcohol preferably used in the present invention is, for example, n-butanol,
Isobutanol, sec-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, isooctanol, n-nonanol, n-decanol, n-dodecanol, n-hexadecanol (cetyl Alcohol), n-octadecanol (stearyl alcohol), 10 to 3 carbon atoms
Alcohols derived from polymers of olefins having 2 to 6 carbon atoms, such as alcohols derived from 0 linear alpha olefins and mixtures thereof, alcohols derived from polypropylene and polybutylene (eg,
Polypropylene alcohol having about 9 to 100 carbon atoms,
Polybutylene alcohol having up to about 100 carbon atoms) and the like, but is not limited thereto. Preferably, it is an alcohol having 1 to about 30 carbon atoms, more preferably about 2 to 24 carbon atoms, and most preferably about 4 to 12 carbon atoms.
Particularly preferred aliphatic alcohols are butanols.

The phenol of the formula (IX) may be a monoalkyl-substituted phenol or a dialkyl-substituted phenol. The monoalkyl-substituted phenol preferably has an alkyl substituent particularly at the para position. The alkyl group of the alkylphenol preferably has 1 to about 30 carbon atoms, more preferably has 2 to 24 carbon atoms, and most preferably has about 4 to 12 carbon atoms. Representative examples of the phenol compound suitably used in the present invention include phenol, methylphenol, dimethylphenol, ethylphenol, butylphenol, octylphenol,
Examples include, but are not limited to, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tetracosylphenol, hexacosylphenol, triacontylphenol. Further, a mixture of alkylphenols such as a mixture of alkylphenols having 14 to 18 carbon atoms, a mixture of alkylphenols having 18 to 24 carbon atoms, a mixture of alkylphenols having 20 to 24 carbon atoms, or a mixture of alkylphenols having 16 to 26 carbon atoms. Can also be used. In particular, an alkylphenol obtained by alkylating phenol with a polymer or oligomer of an olefin having 3 to 6 carbon atoms such as polypropylene or polybutane is preferable.

The polymer is usually comprised of about 8 to about 8 carbon atoms.
100, preferably a polymer having about 10 to 30 carbon atoms. Particularly preferred alkylphenols are those obtained by alkylating phenol with a propylene polymer having an average number of units of four. This propylene polymer is generally known by the name of propylene tetramer and is commercially available.

As noted above, the poly (oxyalkylene) aromatic esters of the present invention have a polyamine moiety covalently connected to the aromatic ring through one of the amine nitrogen atoms. Preferably, the polyamine moiety is derived from a polyamine having about 2 to 12 amine nitrogen atoms and about 2 to 40 carbon atoms. It is particularly preferred that the carbon: nitrogen ratio in the polyamine be in the range of 1: 1 to about 10: 1.

When the compound of the present invention is synthesized using various polyamines containing various nitrogen atoms which are not positionally equivalent, a plurality of substituent isomers are conceivable, and any of them is included in the present invention.

The polyamine may have a linear or branched structure, a cyclic or non-cyclic structure, or a combination thereof. Generally, it is preferred that the amine nitrogens of such polyamines be separated from each other by at least two carbon atoms. Therefore, a polyamine having an aminal structure is not suitable for the present invention. The polyamine may have one or more oxygen atoms, for example, as an ether or a hydroxyl group.

Compounds particularly preferably used in the present invention as polyamines are polyalkylene polyamines such as alkylenediamine. Typical polyalkylene polyamines have about 2 to 12 nitrogen atoms and about 2 to 12 nitrogen atoms.
It contains 24 carbon atoms. About 2 carbon atoms
Preferred are those having up to 6 carbon atoms, and more preferred are those having about 2 to 4 carbon atoms. Examples of such polyalkylene polyamines include ethylenediamine, propylenediamine, isopropylenediamine, butylenediamine,
Pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, diisopropylenetriamine, dibutylenetriamine, di-sec-butylenetriamine, triethylenetetramine, tripropylenetetramine, triisobutylenetetramine, tetraethylenepentamine, pentaethylenehexamine , Dimethylaminopropylamine, and mixtures thereof.

Particularly preferred polyalkylene polyamines are those represented by the following formula:

[0084]

Embedded image H ₂ N— (R ₆ NH) _z —H

(R ₆ is a linear or branched alkylene group having about 2 to 6, preferably about 2 to 4, more preferably about 2 carbon atoms (eg, ethylene: —CH ₂ CH ₂
-), And z represents an integer of 1 to about 4, preferably 1 or about 2)

That is, a particularly preferred polyalkylene
The polyamine is ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, more preferably ethylenediamine and diethylenetriamine, and most preferably ethylenediamine.

[0087] Cyclic polyamines having one or more 5- or 6-membered rings can also be used in the present invention. Examples of such cyclic polyamines include piperazine, 2-methylpiperazine, N- (2-aminoethyl) piperazine, N-
(2-hydroxyethyl) piperazine, 1,2-bis (N-piperazinyl) ethane, 3-aminopyrrolidine,
N- (2-aminoethyl) pyrrolidone and the like can be mentioned. Of these, piperazines are preferred.

Many of the polyamines suitable for use in the present invention are commercially available, and some are not.
Many of them can be synthesized by well-known methods. For example, for the synthesis of amines and their reactions, see Sidgewick's TheOrganic Chemistry of Nitr.
ogen "(Clarendon Press, Oxford, 1966),
Noller's Chemistry of Organic Compounds (Saunde
rs, Philalphia, 2nd edition, 1957), Kirk / Osmer, Encyclopedia of Chemical Technology.
(2nd edition, Volume 2, pages 99-116) and the like.

A polyamine-containing poly (oxyalkylene) aromatic ester in which R ₄ is a hydrogen atom in the formula (I) can be synthesized from a compound of the following formula (X).

[0090]

Embedded image

(W, R ₂ , R ₃ and y have the same meaning as described above.)

The compound of the formula (X) can be prepared by reacting the compound of the formula (VI) with R
A compound in which ₇ is a reactive hydrocarbyl group such as a benzyl or t-butyl group can be obtained by removing the hydrocarbyl group under a suitable reaction condition and converting it to a hydroxyl group. For example, compounds in which R ₇ is a benzyl group in formula (VI) can be obtained from benzyl alcohol using metal salt (VII) by the method described above. The resulting benzyl ether can be cleaved by conventional hydrogenolysis to give a compound of formula (X). Similarly, other reactive hydrocarbyl groups, such as t-butyl groups, can be utilized for compounds having functional groups, such as nitro groups, that are incompatible under hydrogenolysis conditions. t-Butyl ether is cleaved under acidic conditions such as trifluoroacetic acid.

The polyamine-containing poly (oxyalkylene) aromatic ester in which R ₄ is an acyl group in the formula (I) is represented by the following formula (XI).

[0094]

Embedded image

(R ₁ , R ₂ , R ₃ and y have the same meaning as described above, and R ₁₀ is an acyl group represented by the following formula)

[0096]

Embedded image

(R ₅ has the same meaning as described above)

The compound of the formula (XI) can be obtained from the compound of the formula (X) by acylating the terminal hydroxyl group of the poly (oxyalkylene) moiety with a suitable acylating agent. As the acylating agent, acid halides such as acid chlorides and acid bromides, and carboxylic anhydrides are used. Preferred acylating _{agents, R 5 C (O) -V} ( provided that, R ₅ is from 1 to about 30 carbon atoms, preferably about 4 to 1
2, an alkyl group, V represents chlorine or bromine), and an acid halide derivative of the above-mentioned aromatic carboxylic acid (IV). R ₅ C
Examples of the acylating agent represented by (O) -V include acetyl chloride, propionyl chloride, butanoyl chloride, pivaloyl chloride, octanoyl chloride, decanoyl chloride and the like.

The acylation of the compound (X) is carried out by reacting the compound (X)
In an inert solvent such as toluene, dichloromethane, diethyl ether at a temperature of about 25 ° C. to 150 ° C. for about 0.5 to 4
The reaction can be performed for 8 hours. If an acid halide is used as the acylating agent, a sufficient amount of the amine to neutralize the acid formed during the reaction, e.g.,
Triethylamine, di (isopropyl) ethylamine,
The acylation is preferably performed in the presence of pyridine, 4-dimethylaminopyridine, or the like.

The polyamine-containing poly (oxyalkylene) aromatic ester of the present invention may be a poly (oxyalkylene) aromatic ester of the formula (VI) or a compound of the formula (X) (or an acylated compound of the formula (X)) And a suitable polyamine such as the above-mentioned polyamine of the formula (II).

The reaction between a compound of formula (VI) or (X) and a compound of formula (II) will be apparent to those skilled in the art. Aromatic nucleophilic substitution with amines is described in J. Am. F. Vannet, R.A. E. FIG. Zahler, Chemical Review 49,
273-319 (1951). The reaction can be carried out, for example, by reacting compound (VI) with 1 to about 25 equivalents of a polyamine of formula (II) in an inert solvent such as toluene or chloroform or without a solvent at a temperature of about 25 ° C to 175 ° C. For about 0.5 to 48 hours. This reaction can be performed in the presence of a tertiary amine such as triethylamine or diisopropylethylamine to neutralize an acid generated during the reaction. Further, neutralization may be performed using an excess of polyamine. The use of excess polyamine can also minimize the formation of bisaromatic polyamines.

[Fuel Composition] The polyamine-containing poly (oxyalkylene) aromatic ester of the present invention comprises an engine,
In particular, it is useful as an additive to be added to hydrocarbon fuel in order to prevent and suppress accumulation of deposits in the intake valve. Polyamine-containing poly (oxyalkylene) of the present invention
The fuel composition to which the aromatic ester has been added can suppress generation of deposits in the internal combustion engine. The concentration required to achieve the desired level of deposit formation will vary depending upon the type of fuel used, the type of engine, or the presence of other additives.

[0103] The concentration of the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention in the hydrocarbon fuel generally ranges from about 50 to 2500 ppm, preferably from about 75 to 1000 ppm, by weight. If other deposit control additives are present, smaller amounts of the additives of the present invention may be used.

The polyamine-containing poly (oxyalkylene) aromatic ester of the present invention has a boiling point of about 65 ° C. (1 ° C.).
It can also be used as a concentrate using an inert lipophilic (i.e., soluble in gasoline) organic solvent in the range of 50 ° F to about 205 ° C (400 ° F). As the organic solvent, hydrocarbons such as benzene, toluene, xylene, high-boiling aromatic hydrocarbons and aromatic solvents can be used. In addition to this hydrocarbon solvent, aliphatic alcohols having about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol and n-butanol, can also be used. The concentration of the additive in the concentrate is generally about 10 to 70% by weight, preferably about 10 to 50% by weight, and more preferably about 20 to 40% by weight.

In the case of gasoline fuel, other additives may be contained in addition to the additives of the present invention. For example, oxygenating agents such as t-butyl methyl ether, anti-knocking agents such as methylcyclopentadienyltricarbonylmanganese, and dispersing / cleaning agents such as hydrocarbylamine, hydrocarbylpoly (oxyalkylene) amine, and succinimide exist. And may further contain an antioxidant, a metal deactivator, a demulsifier and the like. In the case of diesel fuel, well-known additives such as pour point depressants, flow improvers, and cetane number improvers may be used in combination.

A non-volatile fuel-soluble carrier liquid may be used together with the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention. This carrier liquid is a chemically inert hydrocarbon-soluble liquid medium that significantly increases the non-volatile residue (NVR), and does not significantly increase the octane requirement, but does not significantly increase the octane requirement. It is a liquid component. Various natural oils and synthetic oils can be used as such a supporting liquid. For example, mineral oil, refined petroleum, synthetic polyalkanes and alkenes. Examples of synthetic polyalkanes and alkenes include hydrogenated and non-hydrogenated polyalphaolefins, synthetic polyoxyalkylene derived oils (eg, US Pat.
No. 91537 [Lewis], polyesters (for example, US Pat. No. 3,756,793 [Robinson], US Pat. No. 5,500,478 [Bogel et al.],
European Patent Application No. 356726 [May 7, 1990] and No. 382159 [August 16, 1990]).

It is considered that the above-mentioned carried liquid functions as a carrier of the fuel additive of the present invention, and functions to prevent accumulation of deposits and to remove deposits. When the carrier liquid is used in combination with the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention, accumulation of deposits due to a synergistic effect can be suppressed.

The carrier liquid is generally used in a weight ratio of about 100 to 5000 ppm, preferably about 400 to 3000 ppm, based on the hydrocarbon fuel. The ratio of the loading liquid to the deposit formation suppressing additive is about 0.5: 1 to 1
A range of 10: 1 is preferred, more preferably a range of 1: 1 to about 4: 1, and most preferably about 2: 1. When the carrier liquid is used in a fuel concentrate, its amount is generally about 20-60% by weight, preferably about 30-50% by weight.

[0109]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 A compound represented by the following formula was synthesized.

[0111]

Embedded image

4-fluorobezoyl chloride (20.0 g)
With α-hydroxy-ω-4-dodecylphenoxypoly (oxybutylene) having an average of 20 oxybutylene units [Example 6 of U.S. Pat. No. 4,160,648.
Synthesized by the method described in 1) above, and 221.7 g of the mixture were added to anhydrous toluene (1 L). Furthermore, after adding 4-dimethylaminopyridine (16.1 g), the obtained mixture was heated and refluxed for 16 hours under a nitrogen atmosphere. After cooling to room temperature, 2 L of diethyl ether was added, and the organic layer was washed twice with a saturated aqueous solution of sodium hydrogen carbonate and once with a saturated saline solution. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed under reduced pressure to give the target compound as a yellow oil.
21.1 g were obtained.

Example 2 A compound represented by the following formula was synthesized.

[0114]

Embedded image

A magnetic stirrer, a dropping funnel,
Ethylenediamine (10.2 mL) and the compound synthesized in Example 1 (20.0 g) were placed in a flask equipped with a reflux condenser and a nitrogen gas inlet, and mixed. The mixture was heated at reflux for 16 hours, cooled to room temperature,
Dilute with mL of diethyl ether. The organic layer was washed once with a saturated aqueous solution of sodium hydrogen carbonate, twice with water, and once with saturated saline. After drying over anhydrous sodium sulfate and filtration, the solvent was removed under reduced pressure to obtain 18.3 g of an oil. The oil obtained is subjected to silica gel chromatography, initially hexane / ethyl acetate (7: 3).
Develop with a mixed solvent, then hexane / diethyl ether /
Methanol / isopropylamine (40:40:15:
5) The mixture was developed with a mixed solution to give the target substance as a colorless oil in 10.2.
g was obtained. ¹ H-NMR (CDCl ₃ , D ₂ O) δ: 7.8
5 (d, 2H), 7.1-7.3 (m, 2H), 6.7
5-6.85 (m, 2H), 6.55 (d, 2H),
5.05-5.15 (m, 1H), 3.0-4.0
(M, 4H), 3.15-3.7 (m. 62H), 3.
0 (t, 2H), 0.6-1.8 (m, 125H).

[Example 3]-Single cylinder engine test-The sample compound was added to gasoline, and the deposit formation suppression performance was examined by an ASTM / CFR single cylinder engine test.
The engine used was a Walkershire CFR single cylinder engine. After operating the engine for 15 hours, the intake valve was removed, washed with hexane, weighed, and the difference from the previously weighed clean valve was determined to estimate the amount of deposits generated. The lower the amount of sediment produced, the better the additive. The test conditions are as follows. Water cooling jacket temperature: 93 ° C (200 ° F), degree of vacuum: 305 mmHg
(12 inHg), air-fuel mixture ratio: 12, ignition timing: 400 BTC, rotation speed: 1800 rpm, crankcase oil (lubricating oil): commercially available 30 W lubricating oil.

The amount of carbonaceous deposits adhering to the intake valve determined by the above measurement is shown in Table 1 below in mg.

[0118]

[Table 1] Table 1-Deposits adhering to the intake valve Amount (mg) Sample 1st 2nd Average ──────────────────────────────────── Base oil fuel Only 246.4 253.1 249.8 Example 2 added 3.7 0.6 2.2 ─────────

The base oil fuel used in the above-mentioned single cylinder engine test was unleaded regular gasoline containing no fuel detergent. To this base oil fuel, a sample compound was added in an amount of 75 ppm. The results in Table 1 show that the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention (Example 2) significantly reduces deposits adhering to the intake valve compared to the case of using only the base oil fuel. I understand.

[0120]

According to the polyamine-containing poly (oxyalkylene) aromatic ester of the present invention, the amount of deposits that accumulate inside the engine, particularly, the amount of deposits that accumulate in the intake valve section can be extremely effectively reduced.

Claims (25)

[Claims] 1. A compound represented by the following formula and a fuel-soluble salt thereof: (R ₁ represents a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms, wherein the polyamine moiety is connected to the aromatic ring through one of the amine nitrogen atoms; ₂ and R ₃ are each independently —O—CHR ₂ —CHR ₃ — units, and independently of each other,
R ₄ represents a hydrogen atom, an alkyl group having 1 to 100 carbon atoms, a phenyl group, an aralkyl group having 7 to 100 carbon atoms, a carbon atom having 7 carbon atoms; Represents an alkaryl group of １００100 or an acyl group of the following formula; y represents an integer of 5１００100) (R ₅ represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, an aralkyl group having 7 to 36 carbon atoms, or an alkaryl group having 7 to 36 carbon atoms). 2. The compound according to claim 1, wherein y is an integer of 8 to 50. 3. The compound according to claim 2, wherein y is an integer of 10 to 30. 4. The compound according to claim 1, wherein R ₁ is a polyamine moiety derived from ethylenediamine or diethylenetriamine. 5. The compound according to claim 4, wherein R ₁ is a polyamine moiety derived from ethylenediamine. 6. The compound according to claim 1, wherein R ₄ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms. 7. The compound according to claim 1, wherein one of R ₂ and R ₃ is a lower alkyl group having 1 to 3 carbon atoms, and the other is a hydrogen atom. 8. The compound according to claim 7, wherein one of R ₂ and R ₃ is a methyl group or an ethyl group, and the other is a hydrogen atom. 9. The compound according to claim 6, wherein R ₄ is an alkylphenyl group having an alkyl group having 4 to 12 carbon atoms. 10. A compound represented by the following formula or a fuel-soluble salt thereof, comprising, as a main component, a hydrocarbon having a boiling point in the range of gasoline or diesel oil and effective in suppressing the generation of engine deposits. A fuel composition containing: (R ₁ represents a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms, wherein the polyamine moiety is connected to the aromatic ring through one of the amine nitrogen atoms; ₂ and R ₃ are each independently —O—CHR ₂ —CHR ₃ — units, and independently of each other,
R ₄ represents a hydrogen atom, an alkyl group having 1 to 100 carbon atoms, a phenyl group, an aralkyl group having 7 to 100 carbon atoms, a carbon atom having 7 carbon atoms; Represents an alkaryl group of 〜100 or an acyl group of the following formula; y represents an integer of 5１００100) (R ₅ represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, an aralkyl group having 7 to 36 carbon atoms, or an alkaryl group having 7 to 36 carbon atoms). 11. The method of claim 1, wherein y is an integer from 8 to 50.
0. The fuel composition according to item 0. 12. The fuel composition according to claim 11, wherein y is an integer from 10 to 30. 13. The fuel composition according to claim 10, wherein R ₁ is a polyamine moiety derived from ethylenediamine or diethylenetriamine. 14. The fuel composition according to claim 13, wherein R ₁ is a polyamine moiety derived from ethylenediamine. 15. R ₄ is a hydrogen atom, having 1 to 30 carbon atoms.
The fuel composition according to claim 10, which is an alkyl group having 1 to 30 carbon atoms or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms. 16. One of R ₂ and R ₃ has 1 to 1 carbon atoms.
The fuel composition according to claim 10, wherein the lower alkyl group is 3 and the other is a hydrogen atom. 17. The fuel composition according to claim 16, wherein one of R ₂ and R ₃ is a methyl group or an ethyl group, and the other is a hydrogen atom. 18. The fuel composition according to claim 15, wherein R ₄ is an alkylphenyl group having an alkyl group having 4 to 12 carbon atoms. 19. The above compound is added in an amount of 50 to 25 by weight.
11. The fuel composition according to claim 10, comprising 00 ppm. 20. The fuel composition according to claim 10, comprising 100 to 5000 ppm by weight of a fuel-soluble nonvolatile carrier liquid. 21. A method for reducing deposits inside an internal combustion engine, comprising operating the internal combustion engine using the fuel composition of claim 10. 22. A fuel concentrate comprising an inert and stable lipophilic organic solvent having a boiling point in the range of 65 ° C. to 205 ° C. and 10 to 70% by weight of a compound represented by the following formula or a fuel-soluble salt thereof. Stuff. Embedded image (R ₁ represents a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms, wherein the polyamine moiety is connected to the aromatic ring through one of the amine nitrogen atoms; ₂ and R ₃ independently represent a —O—CHR ₂ —CHR ₃ — unit, and each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms; R ₄ represents a hydrogen atom; Represents an alkyl group having 1 to 100 carbon atoms, a phenyl group, an aralkyl group having 7 to 100 carbon atoms, an alkaryl group having 7 to 100 carbon atoms, or an acyl group represented by the following formula; Represents) (R ₅ represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, an aralkyl group having 7 to 36 carbon atoms, or an alkaryl group having 7 to 36 carbon atoms) 23. R ₁ is a polyamine moiety derived from ethylenediamine or diethylenetriamine,
One of R ₂ and R ₃ is a methyl group or an ethyl group, the other is a hydrogen atom, R ₄ is a hydrogen atom, and has 1 to 3 carbon atoms.
0 or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms, and y is 8
23. The fuel concentrate according to claim 22, which is an integer from ~ 50. 24. R ₄ is a hydrogen atom, having 2 to 24 carbon atoms.
24. The fuel concentrate according to claim 23, which is an alkyl group having an alkyl group having 2 to 24 carbon atoms. 25. The method according to claim 24, wherein R ₁ is a polyamine moiety derived from ethylenediamine, and R ₄ is an alkylphenyl group having an alkyl group having 4 to 12 carbon atoms.
A fuel concentrate according to claim 1.